JPH02240138A - Thermotropic liquid crystal polyester-amide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to thermotopic aromatic polyester-amides. The polyester-amides of the present invention are melt moldable and give molded articles with excellent mechanical properties and optical anisotropy.

Conventional technology. 〉 In recent years, the demand for higher performance plastics has been increasing, and various high-performance plastics have been developed and are now on the market.
Among them, thermotropic liquid crystal polymers, which are composed of particularly rigid molecular chains and exhibit optical anisotropy when melted, have low melt viscosity, good processability, and excellent mechanical properties. is attracting attention.

Fully aromatic polyesters are widely known as such liquid crystal polymers, and for example, homobolymers and cobolymers of 4-hydroxybenzoic acid are commercially available. However, 4-hydroxybenzoic acid homopolymer has a melting point that is too high to be melt-molded. Also,
Copolymer made by copolymerizing 4-hydroxybenzooctaic acid with, for example, terephthalic acid and hydroquinone or 4,4'-biphenol has considerably improved processability as described in Japanese Patent Publication No. 47-47870. Its melting point is still extremely high at 400°C or higher, making it difficult to melt and mold, and its mechanical properties are by no means excellent.

Liquid crystalline aromatic polyamides (aramids) have also been developed and are known as polymers with excellent mechanical properties, but these polymers are of the lyotropic liquid crystal type and cannot be molded in a molten state.

[Problems to be Solved by the Invention] The object of the present invention is to create a new thermoplastic resin that is easy to melt-process and has excellent mechanical properties, particularly high strength, high elasticity, and oscillation properties.・Providing Pick aromatic polyester-amide.

More specifically, the material is processed by thermoplastic molding in a liquid crystal state at a temperature of 400° C. or lower to form a high-strength molded product.

Means for Solving the Problems As a result of extensive studies, the present inventors have discovered an aromatic polyester-amide having a specific repeating unit that achieves the above object.

That is, the present invention provides the following (1), (2), (3), (
The repeating units shown in 4) and (5) are used as constituent components, and fi
The t-position (1) is 20-70 mol% of the total, the unit (2) is 10-30 mol% of the total, and the unit (3) is 5-
25 mol %, unit (4) contains 5-25 mol % of the total, unit (5) contains 0-20 mol 96 of the total, the total of all monomers is 100 mol %, (flow start temperature + 20 mol %)
The present invention relates to an aromatic polyester-amide having a melt viscosity of 10-100,000 poise, determined at a shear rate of 10'sec-' at a temperature of -400°C).

The monomer constituting the repeating r-position (1) is composed of an aromatic hexahydroxycarboxylic acid or a derivative thereof, and Ar represents a divalent A aromatic ring having 6 to 18 carbon atoms. An example of such an aromatic ring is a hat. The hydrogen atoms on these aromatic rings can be further converted into 1 by an anokyl group, an alkoxy group, a phenyl group, or a halogen.
More than one may be replaced. Specific examples include p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4.
Examples include 4°-hydroxybiphenylcarboxylic acid or derivatives thereof.

The monomer constituting the repeating unit (2) is 2.6-
Naphthalene dicarboxylic acid or its derivatives can be mentioned. One or more hydrogen atoms on the aromatic ring may be further substituted with an alkyl group, an alkoxy group, a phenyl group, a halogen, or the like.

The monomer occupying the repeating r1t position (:u) represents an aromatic monomer capable of forming an amide bond in the polymer. Specific examples include p-aminophenol, p-N-methylaminophenol, p-phenylenediamine, m-
Examples include aminophenol, m-phenyl diamine, 4,4°-diaminodiphenyl ether, and the like.

The monomer constituting repeat position 11j (4) is 4.4゛-biphenol.

The monomer constituting the repeating unit (5) is composed of aromatic dicarboxylic acid and derivatives thereof, and A'
represents a divalent aromatic ring having 6 to 18 carbon atoms. Examples of such an 'A8 ring include the following.

One or more hydrogen atoms on these aromatic rings may be substituted with an alkyl group, an alkoxy group, a phenyl group, a halogen, or the like. Specific examples include terephthalic acid,
Isophthalic acid, 4.4°-diphenyldicarboxylic acid 4
．． Examples include 4°-diphenyl ether dicarboxylic acid.

The amount of repeating unit 11 (2) is 10-30 mol% of the total, and if the repeating unit (2) exceeds 30 mol%, the melting point of the obtained polymer will be very low, and the heat resistance of the polymer will be reduced. gender becomes low. If the amount is less than 10 mol %, the melting point of the polymer will become very high, making melt processing difficult and vibration damping properties lower, which is not preferable.

The amount of repeating unit (3) is 5-25 mol% of the total,
If the content of the repeating unit (3) exceeds 25 mol %, the melting point of the resulting polymer will be extremely high, and the addition property of the polymer will deteriorate. If the amount is less than 5 mol %, a polymer with excellent melt processability can be obtained, but its mechanical properties are low and this is not preferable.

The middle repeating components (2) and (4) are essential components for imparting damping properties to this polymer.

In the thermotropic liquid crystal polyester-amide of the present invention, the terminal groups may be optionally capped. As capping agents, aromatic monohydroxy compounds such as 4-hydroxydiphenyl and 4-nonylphenol are used for acid end groups, and aromatic monocarboxylic acid compounds such as diphenylcarboxylic acid and naphthalenecarboxylic acid are used for hydroxyl end groups. It will be done.

The boester-amide of the present invention has (flow onset temperature +20
When the melt viscosity is measured at a shear rate of 103 sec at a temperature of -400°C, it shows a value of 10-100,000 poise, especially 10-11. Those exhibiting a melt viscosity of 0 0 0 0 poise are preferred. This constant melt viscosity is
The test can be carried out using a Koka type flow tester manufactured by Shimadzu Corporation, and a die having a diameter Q of 5 mm and a length of 2 mm.

The polyester-amide of the present invention can be produced according to the conventional polymerization method for aromatic polyester, and there are no particular restrictions on the production method, but typical production methods include, for example,
4-hydroxybenzoic acid, 4,4゛-biphenol, p
- A method of reacting a lower acyl ester of aminophenol, preferably an acetate ester, can be mentioned. Acyl esters can also be made in situ and used without isolation.

To be more specific about this reaction, repeating units (1
), (2), (3), (4), and (5) and an active esterifying agent such as acetic anhydride, a polymerization device equipped with a stirrer, a nitrogen gas introduction pipe, and a vacuum distillation device. and heated under a nitrogen stream at room temperature to 150°C for 30 minutes to 15 hours to effect active esterification of hydroxyl groups. After this, 180-
React at a temperature of 50°C. Polycondensation reactions generally involve 4
It is preferred to carry out the polycondensation at relatively high 1M since the rate increases with increasing temperature. However, at high temperatures polyester-amides tend to decompose. Further, a higher molecular weight is advantageous for thermal stability.

Therefore, it is generally desirable to start the reaction at a low temperature and to continuously increase the temperature as the reaction progresses. Also,
If the reaction rate decreases, the reaction can be carried out under reduced pressure of about 1 mm Hg.

The product obtained is, in some cases, 200-30
Solid phase coalescence can be carried out at a temperature of 0°C.

This operation increases the molecular weight and significantly improves the properties of the resulting polymer.

Additionally, a catalyst can be used to promote the above reaction. This type of probe is known, and includes, for example, alkali metal salts, Mn, Mg, Zn, Cd. sb compounds, etc.

The amount of catalyst is 0.0% relative to the amount of total monomers used. 0
0 1 - 1. 0, particularly preferably 0.01-0.2% by weight.

Effects of the Invention The thermotropic aromatic polyester-amide of the present invention has a low molding temperature of 400°C or less and a relatively low melt viscosity, so it can be used in conventional methods such as injection molding, extrusion molding, compression molding, and blow molding. It can be subjected to melt molding and processed into molded products, fibers, films, etc. Furthermore, this polyester-amide achieves molecular orientation due to shearing force during processing, and therefore provides molded products with high strength, high elasticity, and excellent -j-method stability. Furthermore, this polymer has the characteristic of being excellent in damping properties near room temperature. Take advantage of these characteristics! As another application field,
Examples include the mechanical, electrical, and electronic fields that utilize heat resistance and high strength, and the Icheon field that utilizes vibration damping properties and high elasticity, such as speakers. In addition, reinforcing agents such as glass fiber and carbon fiber are added to the polyester-amide of the present invention during molding.
Additives such as fillers, nucleating agents, pigments, antioxidants, stabilizers, and other thermoplastic resins can be added to improve the properties of the molded article.

EXAMPLES> The present invention will be explained in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited by these Examples either. The outflow start temperature was 6°C under a pressure of 100 Kg/cd using a Koka type flow tester using a die with a length of 10 mm and a diameter of 1 mm.
/min, and the melt viscosity reached 4800.
0 poise! The temperature was set to 1.

The melting temperature of the obtained polymer was determined by DSC to be 10°C/
It was determined by rn i n.

The anisotropy of the obtained polymer during melting was confirmed using a polarizing microscope equipped with a Ho-So 1 stage.

The damping properties of the obtained polymer were judged by tan δ based on the dynamic viscoelasticity ΔIII constant.

The physical properties of the obtained polymer were determined by bending the polymer into a test piece,
It was injection molded into a tensile test piece and measured according to ASTM standards.

Example 1 690 g (5 moles) of p-hydroxybenzoic acid and 540 g (5 moles) of 2,6-naphthalene dicarboxylic acid were placed in a polymerization apparatus equipped with a stirrer, a nitrogen gas inlet tube, and a condenser.
2.5 mol), p-aminophenol 164 g (1
．． 5 mo, le), 186 g of 4.4' biphenol (
After charging 1 122 g (11 mol) of acetic anhydride and purging with nitrogen, the temperature of the polymerization apparatus was raised to 150°C while flowing nitrogen, and held for 2 hours to activate hydroxy groups and amino groups. I do. Thereafter, the reaction temperature was raised to 350° C. while distilling off the by-product acetic acid. After the reaction was allowed to proceed at 350° C. for 1 hour, the pressure of the reaction system was gradually reduced to about 2 m tn H g and maintained for 1 hour, and then the reaction was completed. The polymer was taken out after cooling the polymerization system.

This polymer showed a melting endothermic peak at 298°C by DSC measurement. Optical anisotropy was shown by in-iltll determination using a polarized light microscope. The starting temperature of the outflow was 272°C.

At a temperature of 310°C and a shear rate of IQ'sec-' it! The constant melt viscosity was 1800 poise.

Regarding vibration damping properties, the results of dynamic viscoelasticity measurements are shown in Figure 11. Its tan δ is 0.067 near chamber 'rM.
Met.

The physical properties are shown in Table-1.

Example 2 Into the assembly apparatus described in Example 1, 690 g (5 mol) of p-hydroxybenzoic acid, 648 g (3 mol) 2,6-naphthalene dicarboxylic acid, and 108 g (1 mol) p-diaminobenzene were added. ), 372 g (2 moles) of 4,4゛-biphenol, and 1234 g (12 moles) of acetic anhydride.
．． 1 mol) was charged, and polymer synthesis was performed in the same manner as in Example M1.

The melting temperature determined by osc apt was 332°C.

Observation using a polarizing microscope showed optical anisotropy in the molten state. The starting temperature of the outflow was 307°C.

The melt viscosity measured at a temperature of 330°C and a shear rate of 103 sec-' was 3200 poise.

Regarding vibration damping properties, Figure 2 shows the results of dynamic viscoelasticity measurements. Its tan δ was 0.063 near the chamber.

The physical properties are shown in Table-1.

Comparative Example 1 In the polymerization apparatus described in Example 1, 690 g (5 moles) of p-hydroxybenzoic acid, 540 g (2.5 moles) of 2.6-naphthalene dicarboxylic acid, and 164 g (1 mole) of p-aminophenol were added. .5 mol) Hydroquinone 1
10g (1 mol), 1122g (11 mol) of acetic anhydride
was charged, and a polymer was synthesized in the same manner as in Example 1.

The melting tolerance determined by DSC ilPI was 338°C.

Observation using a single-light microscope showed optical anisotropy in the molten state. The starting temperature of the outflow was 321°C.

The melt viscosity measured at a temperature of 350° C. and a shear rate of 103 sec-' was 2900 poise.

Regarding nil vibration, the results of dynamic viscoelasticity measurement are shown in Figure 13.
Shown below. Its tan δ is 0.048 near room temperature, which is not very good.

Regarding the physical properties, the results are shown in Table-1.

Comparative Example 2 In the polymerization apparatus described in Example 1, 690 g (5 moles) of p-hydroxybenzoic acid and 95 g of terephthal M were added.
(0.56 mol) and 143 g (0.56 mol) of isophthalic acid.
86 mol), p-aminophenol 77g (0.7
1 mole), 132 g of 4.4'-biphenol
(0.71 mol), 890 g (8.6 mol) of acetic anhydride
was charged, and polymer synthesis was performed in the same manner as in Example 1.

No melting temperature or glass transition temperature was observed by DSC measurement. No optical anisotropy was observed under polarized light microscopy. The starting temperature of the outflow was 355°C. l] at a temperature of 380°C and a shear rate of 10'sec'-'? The constant melt viscosity was 8400 poise.

Regarding vibration damping properties, the results of dynamic viscoelasticity measurements are shown in Figure 14. Its tan δ was 0.039 near room temperature.

Regarding the physical properties, the results are shown in Table-1.

Comparative Example 3 In the polymerization apparatus described in Example 1, p-hydroxyammonyl, l
,,4, 690 g (5 mol) of Tani acid, 540 g (2.5 mol) of 2.6-naphthalene dicarboxylic acid, 4,4
- 465 g (2.5 mol) of biphenol and 1122 g (11 mol) of acetic acid were charged, and polymer synthesis was performed in the same manner as in Example IMI 1.

The melting temperature determined by DSC All was 291°C. The starting temperature of the outflow was 268°C. Temperature '3
The melt viscosity determined by 2) at 00°C and a shear rate of 103 sec-' was 1000 poise.

Regarding vibration damping properties, the results of dynamic viscoelasticity measurements are shown in Figure 15. Its tan δ near room temperature was 0.068.

Regarding the physical properties, the results are shown in Table-1.

4 drawings IJf 71 N, N Ming drawings 1 to 5 are 6 examples 1 and 2. FIG. 3 is a diagram showing the dynamic viscoelasticity of polymers obtained in Comparative Example 1, Comparative Example 2, and Comparative Example 3.

Special. :'1 111 people Tosoh Corporation Procedural amendment 5. Target of correction Claims section of the specification and details of the invention Year Month l5 Day field for explanation 6. Contents of correction

Claims (1)

[Claims] (1) Essentially the following (1), (2), (3), (4)
Furthermore, in some cases, the repeating unit shown in (5) is used as a constituent component, -O-Ar-O-(1) ▲Mathematical formula, chemical formula, table, etc.▼(2) -X-Ar-Y-(3 ) (X...NH, Y...NH, O) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(4) -CO-Ar-CO-(5) Contains 20-70 mol% of the unit (1), Unit (2
) is contained in 10-30 mol% of the total, unit (3) is contained in 5-25 mol% of the total, and unit (4) is contained in 5-25 mol% of the total.
mol%, and the unit (5) is present in the respective ranges of 0 to 20 mol% of the total,
The sum of all monomers is 100 mol%, a thermotropic liquid crystal layer is formed at a temperature lower than 400°C, and the temperature is 10^3 sec^- within a temperature of -400°C (outflow start temperature + 20°C).
An aromatic polyester-amide having a melt viscosity of 10-100,000 poise measured at a shear rate of ^1.